EP0859873B1 - Verfahren zur entfernung von zinn - Google Patents
Verfahren zur entfernung von zinn Download PDFInfo
- Publication number
- EP0859873B1 EP0859873B1 EP96938019A EP96938019A EP0859873B1 EP 0859873 B1 EP0859873 B1 EP 0859873B1 EP 96938019 A EP96938019 A EP 96938019A EP 96938019 A EP96938019 A EP 96938019A EP 0859873 B1 EP0859873 B1 EP 0859873B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- bar
- component
- sodium hydroxide
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a method for removing tin from the surface and / or from an area close to the surface of a component.
- the invention further relates to a Application of the method to a component, in particular a Turbine blade.
- EP 0 631 832 A1 describes the production of a component described by directional solidification of a molten metal.
- an alloy melt forming the component is placed in a casting mold filled, the mold in a Heating chamber at a temperature above the melting temperature the alloy is held.
- the mold with the melted Alloy is made by continuous insertion into a bath from a cooling liquid to a directed solidification brought.
- the coolant is a high temperature gradient with a heat-insulating layer of flowable Material covered, through which the mold into the Coolant is lowered.
- molten tin at a temperature of about 260 ° C can be used.
- LMC liquid metal cooling
- the cracks in the mold Liquid metal, especially liquid tin, with the solidified Alloy comes into direct contact.
- it can Tin stick to the surface (tin accumulation) or a connection with the alloy in a region near the surface enter (tin enrichment).
- heat treatment of the cast There is the possibility of further diffusion into the component of tin into the component. This creates the danger the impairment of the mechanical properties and the Corrosion properties of the component.
- DE 36 04 792 A1 describes a process for the production tin-free objects by deep drawing or ironing described by tinned iron sheet.
- a tin topper on a thin sheet for example for the production of Cans, with a strong alkali, such as sodium hydroxide, away.
- FR-A-410 901 describes a method for removing Tin from scrap, especially white metal, is known. With this The process is about in some way to remove the tin from the scrap, indicating damage no reference to the scrap and no consideration becomes. The process is carried out in a closed vessel carried out, the scrap of an alkaline solution, Caustic soda, at a pressure of 7 atmospheres and more as well exposed to a temperature of 150 ° C or more.
- GB-A-190 705 273 relates to a method for removing tin or similar metals from a basic body without the Base body is damaged.
- the procedure is described in a closed vessel carried out with an alkaline Solution, especially with sodium hydroxide solution.
- the procedure is at one temperature of over 100 ° C and in a pressure range between 7 and 15 Atmospheres, i.e. 6 to 14 atmospheric pressure carried out.
- DE-C-325 973 shows a common method of removal of tin, being a particularly effective use of the space a pressure vessel is reached. This happens because that a vertical pressure vessel with 500 1 volume is filled with tinplate and about 70 l of a sodium hydroxide solution be pumped in. However, this means that the sodium hydroxide solution is of some kind Outlet in the upper end of the pressure vessel and due to the Gravitational effect flows through the pressure vessel. This causes wetting of the white metal and removal of tin reached.
- the object of the invention is a method for removal of tin from a surface and / or from a surface Specify the area of a component.
- the object is achieved by a removal method of tin from a surface and / or from one solved near-surface area of a component in which the Component solidified in a bath made of liquid tin and of concentrated sodium hydroxide solution, which was between 30 Wt .-% and 60 wt .-% sodium hydroxide contains at an overpressure between 3 bar and 6 bar and a temperature above 95 ° C. becomes.
- a movement is created in the caustic soda, so that the component is flowed around by the sodium hydroxide solution, which results in a higher tin removal rate than when there is no flow around the component.
- a turbulent flow around the component is advantageous. With In a turbulent flow, the sodium hydroxide solution becomes saturated effective with tin ions on the surface of the component prevented.
- the procedure is at an overpressure carried out, which is 3 to 6 bar.
- the method is preferably in a pressure-resistant Container, a so-called autoclave, feasible, in which a corresponding overpressure can be generated.
- An overpressure of 3 bar means an additional pressure exceeding atmospheric pressure.
- a suitable one Pressure vessel preferably consists of a steel, which compared to concentrated sodium hydroxide solution at high temperatures and is resistant to the specified pressure values.
- the method is preferably used at an overpressure between 3 and 4 bar, in particular 3.5 bar, and a temperature of between 110 ° C and 170 ° C, especially 140 ° C, performed.
- Another advantageous overpressure and temperature combination is at an overpressure between 5 and 6 bar, in particular 5.5 bar, and a temperature between 180 ° C and 240 ° C, especially around 220 ° C.
- That combination is characterized in that directed in the manufacture of a solidified component a treatment of the component anyway in the above combination with concentrated Sodium hydroxide solution for removing deposits from the casting mold he follows. Experiments surprisingly showed the effect that removal of the tin takes place at the same time. A appropriate choice of time for this process, the achievement a flow around the component and / or the maintenance allow a high concentration of the sodium hydroxide solution thus a direct integration of the removal process of tin in the manufacturing process of a component without further additional measures.
- the use of concentrated caustic soda at an elevated Temperature leads to selective detachment or detachment of tin and / or tin-containing phases from one component, other areas of the alloy forming the component through the concentrated sodium hydroxide solution not be attacked. Through the removal process the component remains essentially undamaged from tin and has the desired mechanical properties and the corrosion properties.
- the temperature is over 95 ° C.
- the component becomes the sodium hydroxide solution over a predefinable period of time exposed, the concentration of caustic soda during this period at a largely constant level is held.
- the duration can be several days, especially 11 days.
- the component is preferably immersed in a bath of caustic soda and remains for the predefinable length of time in the bathroom continuously.
- the sodium hydroxide solution used has a percentage by weight (% By weight) from 30% by weight to 60% by weight, in particular 33%, on sodium hydroxide (NaOH).
- the tin removal process is preferably based on a metallic component of a gas turbine plant, in particular a turbine blade, a heat shield of a combustion chamber or a guide ring segment applied.
- the component is in a bath of liquid tin directed frozen.
- the component can, for example, according to one of the production processes such as described in EP-A1 0 631 832 or DE-OS 22 42 111 getting produced.
- the component preferably has a Nickel based alloy, especially a super alloy. For such a component, which is like a turbine blade or a heat shield element increased corrosive and mechanical When exposed to stress, it is special Meaning that the accumulated during production or Alloyed tin is completely removed.
- FIGS. 1-10 In the FIGURE are the area-specific weight loss or Removal rate for various nickel-based alloys shown, which is a concentrated sodium hydroxide solution with 33% by weight Sodium hydroxide at a temperature of 150 ° C and one Overpressure of 3.5 bar were exposed. For all alloys It is clearly evident that weight loss over time increases significantly. Weight loss is highest for a nickel super alloy with a share of 0.07% carbon, 8.1% chromium, 9.2% cobalt, 0.5% molybdenum, 9.5% Tungsten, 3.2% tantalum, 5.6% aluminum, 0.7% titanium, 0.015% Boron, 0.02% zircon, 1.4% hafnium and a remainder of nickel ( Figures in percent by weight).
- the course of weight loss is twice logarithmic above the Plotted time and the measurement curve with the reference number 4 remove.
- the measurement curve with reference number 5 shows one slightly lower area specific weight loss for a nickel superalloy with a share (details in percent by weight) of carbon ⁇ 0.01%, chromium 16%, molybdenum 3%, tantalum 3.5%, aluminum 3.5%, titanium 3.5%, boron ⁇ 0.005%, zircon ⁇ 0.008% and a remainder made of nickel.
- the further one Measuring curve 6 applies to a nickel-tin alloy with 2 % By weight of tin.
- a complete Guaranteed removal of tin which for example at the manufacture of a turbine blade using the method directional solidification and subsequent liquid metal cooling attached to the turbine blade or in one near the surface was alloyed.
- the process can be the manufacturing process of turbine blades be expanded in such a way that there is also a distance of the tin is reachable and thus a possible one Influencing corrosion resistance and strength the turbine blade can be excluded.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- ing And Chemical Polishing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
- Die FIGUR
- zeigt den Abtrag von Zinn für verschiedene Nickel-Basislegierungen.
Claims (10)
- Verfahren zur Entfernung von Zinn von einer Oberfläche und/oder aus einem oberflächennahen Bereich eines Bauteils, das in einem Bad aus flüssigem Zinn gerichtet erstarrt wurde, bei dem das Bauteil von konzentrierter Natronlauge, die zwischen 30 Gew.-% und 60 Gew.-% Natriumhydroxid enthält, bei einem Überdruck zwischen 3 bar und 6 bar und einer Temperatur über 95 °C umströmt wird.
- Verfahren nach Anspruch 1, bei dem eine turbulente Umströmung des Bauteils erzeugt wird.
- Verfahren nach Anspruch 1 oder 2, bei dem der Überdruck zwischen 3 bar und 4 bar sowie die Temperatur zwischen 110 °C und 170 °C liegt.
- Verfahren nach Anspruch 3, bei dem der Überdruck etwa 3,5 bar und die Temperatur etwa 140 °C betragen.
- Verfahren nach Anspruch 1 oder 2, bei dem der Überdruck zwischen 5 bar und 6 bar sowie die Temperatur zwischen 180 °C und 240 °C liegt.
- Verfahren nach Anspruch 5, bei dem der Überdruck etwa 5,5 bar sowie die Temperatur etwa 220 °C betragen.
- Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Natronlauge 33 Gew.-% Natriumhydroxid (NaOH) enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei das Bauteil ein Gasturbinenbauteil ist.
- Verfahren nach Anspruch 8, wobei das Bauteil eine Turbinenschaufel, ein Hitzeschildelement oder ein Führungsringsegment ist.
- Verfahren nach einem der vorhergehenden Ansprüche, bei der das Bauteil eine Nickelbasislegierung aufweist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19538440 | 1995-10-16 | ||
DE19538440 | 1995-10-16 | ||
PCT/DE1996/001962 WO1997014823A1 (de) | 1995-10-16 | 1996-10-16 | Verfahren zur entfernung von zinn |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0859873A1 EP0859873A1 (de) | 1998-08-26 |
EP0859873B1 true EP0859873B1 (de) | 2002-07-24 |
Family
ID=7774952
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96938019A Expired - Lifetime EP0859873B1 (de) | 1995-10-16 | 1996-10-16 | Verfahren zur entfernung von zinn |
Country Status (5)
Country | Link |
---|---|
US (1) | US5993559A (de) |
EP (1) | EP0859873B1 (de) |
AU (1) | AU7560696A (de) |
DE (3) | DE19680889D2 (de) |
WO (1) | WO1997014823A1 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010062316A (ko) * | 1999-12-14 | 2001-07-07 | 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹 | 금속 기판내의 통로 구멍으로부터 피복물을 제거하는방법, 및 이와 관련된 제품 |
US20100147803A1 (en) * | 2008-12-15 | 2010-06-17 | General Electric Company | Process for removing metallic material from casted substates, and related compositions |
US20100147481A1 (en) * | 2008-12-15 | 2010-06-17 | General Electric Company | Methods of manufacturing casted articles, and systems |
US8616077B2 (en) * | 2009-08-05 | 2013-12-31 | United Technologies Corporation | Non-destructive inspection method for metallic alloys |
JP5481179B2 (ja) * | 2009-12-15 | 2014-04-23 | Dowaメタルテック株式会社 | Cu系材料のSnめっき層の剥離方法 |
US8465979B2 (en) | 2011-02-24 | 2013-06-18 | General Electric Company | Method for detecting tin |
EP2503029B1 (de) | 2011-03-22 | 2013-03-20 | Atotech Deutschland GmbH | Verfahren zum Ätzen einer mit Zinn oder einer Zinnlegierung gefüllten vertieften Struktur |
KR101291681B1 (ko) * | 2012-04-10 | 2013-08-05 | 타운마이닝캄파니(주) | 바렐 도금용 스틸볼의 스크랩으로부터 주석 및 니켈을 회수하는 방법 |
CN114622281B (zh) * | 2020-12-11 | 2024-04-12 | 中国科学院金属研究所 | 液态金属冷却定向凝固法制备单晶叶片过程中的低熔点金属污染控制方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190700527A (en) * | 1907-01-08 | 1907-03-28 | Herrmann Lichtenfeld | An Improved Hairdressers' Block |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR410901A (fr) * | 1908-12-17 | 1910-06-02 | Gustav Spitz | Procédé pour la séparation de métaux, solubles dans les alcalis, des déchets et des alliages contenant de tels métaux |
DE325973C (de) * | 1917-11-30 | 1920-09-17 | John Billwiller Dipl Ing | Verfahren zur Entfernung von UEberzuegen von Metallen o. dgl. |
FR584789A (fr) * | 1923-10-27 | 1925-02-13 | Procédé et appareil pour le désétamage des tubes | |
CH108307A (fr) * | 1924-03-05 | 1925-01-02 | Marino Quintin | Procédé pour récupérer les métaux constitutifs du fer-blanc et de pièces étamées. |
US2357970A (en) * | 1942-01-14 | 1944-09-12 | Frank E Rath | Surface treatment of tinned material |
US2711364A (en) * | 1953-12-31 | 1955-06-21 | John G Beach | Polishing metals and composition therefor |
US3121005A (en) * | 1961-03-13 | 1964-02-11 | M & T Chemicals Inc | Process for detinning |
DE1583870B1 (de) * | 1967-08-22 | 1971-05-27 | Council Scient Ind Res | Verfahren zur wiedergewinnung des metallischen zinns aus weissblechabfaellen |
US4164542A (en) * | 1973-05-08 | 1979-08-14 | Pincus Deren | Detinning process |
GB2012815B (en) * | 1978-01-16 | 1982-07-21 | Metal Box Co Ltd | Stripping coatings from articles |
US4687545A (en) * | 1986-06-18 | 1987-08-18 | Macdermid, Incorporated | Process for stripping tin or tin-lead alloy from copper |
US5232619A (en) * | 1990-10-19 | 1993-08-03 | Praxair S.T. Technology, Inc. | Stripping solution for stripping compounds of titanium from base metals |
-
1996
- 1996-10-16 DE DE19680889T patent/DE19680889D2/de not_active Ceased
- 1996-10-16 DE DE1996142732 patent/DE19642732A1/de not_active Ceased
- 1996-10-16 EP EP96938019A patent/EP0859873B1/de not_active Expired - Lifetime
- 1996-10-16 AU AU75606/96A patent/AU7560696A/en not_active Abandoned
- 1996-10-16 DE DE59609489T patent/DE59609489D1/de not_active Expired - Lifetime
- 1996-10-16 WO PCT/DE1996/001962 patent/WO1997014823A1/de active IP Right Grant
-
1998
- 1998-04-16 US US09/061,374 patent/US5993559A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190700527A (en) * | 1907-01-08 | 1907-03-28 | Herrmann Lichtenfeld | An Improved Hairdressers' Block |
Non-Patent Citations (1)
Title |
---|
GMELIN INSTITUT: "GMELINS Handbuch der anorganischen Chemie, System Nummer 46, Lieferung B, Seiten 364-365", 1971, VERLAG CHEMIE, WEINHEIM * |
Also Published As
Publication number | Publication date |
---|---|
AU7560696A (en) | 1997-05-07 |
DE19680889D2 (de) | 1999-03-11 |
EP0859873A1 (de) | 1998-08-26 |
WO1997014823A1 (de) | 1997-04-24 |
DE19642732A1 (de) | 1997-04-17 |
DE59609489D1 (de) | 2002-08-29 |
US5993559A (en) | 1999-11-30 |
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